Fluxant agents for hydrocarbon binders

ABSTRACT

The invention concerns the use as a fluxant agent of at least one compound with the formula (I) 
       R 1 —X—R—Y—R 2   (I)
         where:   R 1  and R 2 , which can be identical or different, are hydrocarbon chains, linear or branched, at C 2 -C 11 ;   each of —X— and —Y—, which can be identical or different, is an —O—(C═O)— group; —(C═O)—O—; —NR′—(C═O)—, where R′ represents a hydrocarbon atom or an alkyl radical at C 1 -C 4 , or —(C═O)—NR′—, where R′ represents a hydrocarbon atom or an alkyl radical at C 1 -C 4 ,   the —R— group is a divalent hydrocarbon chain, at C 1 -C 10 , linear or branched, and possibly interrupted by one or more oxygen atom(s)
 
in a composition including a hydrocarbon binder for the preparation of the bituminous product based on solid mineral particles in contact with the said hydrocarbon binder, where the said compound of formula (I) is present in the said composition when the said composition is brought into contact with the said solid mineral particles.

The present invention relates to the field of fluxant agents forhydrocarbon binders, which can be used in particular in roadconstruction applications. More specifically, the invention concerns theuse as a fluxant agent of a specific volatile compound of formula (I) asdefined below in a composition including a hydrocarbon binder used toproduce a bituminous product based on mineral particles bound togetherby the said composition including the hydrocarbon binder.

In “bituminous” products, mineral particles are bound by a hydrocarbonbinder, in particular a bitumen. The hydrocarbon binders which are usedin bituminous products of this type are very viscous products, typicallyviscoelastic, which to be handled must be heated, emulsified and/or haveadditives added in the form of compounds called “fluxant” compounds, oneeffect of which is to enable their viscosity to be reduced. Thesefluxants can be of petroleum, petrochemical, carbochemical or plantorigin.

Habitual fluxants are the fluxants of petroleum origin which include:

-   -   “petroleum fluxants”, which are products derived from the        distillation of crude oil (light fraction(s)), which may have        been subjected to a hydrotreating operation. One can cite as        examples the fluxant agents sold by Total (Greenflux® 2000,        Greenflux® SD in particular).    -   “petrochemical fluxants”, which are products derived from the        distillation of crude oil (light fraction(s)), having been        subject to at least one thermal cracking operation and        additional distillation. One can cite as an example the fluxant        agents sold by VFT France (Adheflux®).

Such fluxants of petroleum origin are very satisfactory in terms ofresults. Indeed, when they are added to a hydrocarbon binder they enableits viscosity to be reduced from time to time, whilst ensuring generallythat the mechanical properties of the bituminous product based on thisfluxed hydrocarbon binder are not significantly impaired, and thus makethem fit for their use for roads, in particular with a sufficientcohesion increase.

These fluxants of petroleum origin are volatile products: after they areincorporated in the hydrocarbon binder where they reduce the viscosityas desired they evaporate, causing the binder to recover its originalcharacteristics appreciably. However these released fluxants have manynegative environmental impacts. In addition, their use is dangerous anduncomfortable (harmful and unpleasant vapours, and danger offlammability).

Other volatile fluxant agents are the fluxants of carbochemical origin,which are products derived from pyrolysis of carbon, after being subjectto at least one distillation operation, which have the majordisadvantage that they are recognised carcinogens.

To replace the above-mentioned volatile fluxants, fluxants have beenproposed of natural, non-fossil origin (plant or animal origin), whichenable the release of harmful volatile organic compounds to be avoided.A fluxant of non-fossil natural origin is a non-fossil natural oil, oneof its derivatives such as the esters of fatty acid, or a blend of twoor more of these oils and/or oil derivatives. One can cite in particularthe plant oils such as the oils of sunflower, rapeseed, groundnut,copra, flax, palm, soya, olive, castor, corn, marrow, grape pips,jojoba, sesame, walnut, hazelnut, tung oil, tall oil, their derivatives,and blends of them. Most of these oils consist essentially of fattyacids at least with unsaturated C₁₆. Such fluxants are, for example,described in applications FR 2 910 477, EP 0 900 822, FR 2 721 043 or FR2 891 838.

With non-volatile fluxants of the type of the above-mentioned oils, theincrease in consistency of the binder in the final product (afterspreading or after coating) is not accomplished by evaporation, unlikewith volatile fluxants, but rather by cross-linking, typically afterradical reactions, with the unsaturated fatty chains reacting in thepresence of airborne oxygen. These reactions, which can be catalysed bythe addition of drying agents such as metal salts, include the formationof —O—O— peroxide bridges on the unsaturated chains. These bridges areunstable and lead to the formation of free radicals, which willthemselves react with other unsaturations of other chains. Thistechnique of cross-linking of the fluxant thus applies only tounsaturated compounds. The fluxant is selected on the basis of theiodine index which characterises the rate of unsaturations of acompound, and therefore its ability to react by siccativation.

Although they have lesser effects on the environment and the well-beingand health of those handling them, fluxants of non-fossil natural originare, however, less satisfactory than fluxants of petroleum origin interms of results. Indeed, the results in terms of cohesion increase areless satisfactory. They usually lead to disorders in the case ofshowers, heat or excessively dense traffic, problems of bleeding,related in particular to poor adhesion of the fluxed hydrocarbon binderto the solid mineral particles.

Bituminous products based on bitumen fluxed with fluxants of non-fossilnatural origin are thus currently considered to be not suitable formoderate to dense traffic with climatic variations.

One aim of the invention is to provide a solution:

-   -   enabling the viscosity of a hydrocarbon binder to be reduced    -   enabling a hydrocarbon binder of wettability which is suitable        with regard to solid mineral particles to be obtained    -   without having the above-mentioned disadvantages

To this end, it is proposed according to the present invention to use,as fluxants, specific compounds, concerning which the inventors have nowdiscovered, in the course of the work which led to the presentinvention, (1) that they behave as interesting volatile fluxants which,after being incorporated in compositions including a hydrocarbon binder,and before their evaporation, enable the viscosity of the hydrocarbonbinder to be reduced, which can consequently be used more easily, butwithout having the disadvantages of habitual volatile fluxants, in termsof impact on the environment and toxicity for their handler; and (2)that they also lead for the composition to a satisfactory wettabilitywith regard to solid mineral particles, of the same order as thewettabilities of the best fluxant agents currently used, such asGreenflux® SD, which in particular allows satisfactory adherence to thesolid mineral particles.

Another object of the invention is the use, as a fluxant agent, of atleast one compound with the formula (I)

R¹—X—R—Y—R²  (I)

-   -   where:    -   R¹ and R², which can be identical or different, are hydrocarbon        chains, linear or branched, at C₂-C₁₁;    -   each of —X— and —Y—, which can be identical or different, is an        —O—(C═O)— group;    -   —(C═O)—O—; —NR′—(C═O)—, where R′ represents a hydrocarbon atom        or an alkyl radical at C₁-C₄, or (C═O)—NR′—, where R′ represents        a hydrocarbon atom or an alkyl radical at C₁-C₄,    -   the —R— group is a divalent hydrocarbon chain, at C₁-C₁₀, linear        or branched, and possibly interrupted by one or more oxygen        atom(s)        in a composition including a hydrocarbon binder for the        preparation of a bituminous product based on solid mineral        particles in contact with the said hydrocarbon binder, where the        said compound of formula (I) is present in the said composition        when the said composition is brought into contact with the said        solid mineral particles.

According to the invention, it is possible to use a single compound offormula (I) or alternatively a blend of several compounds of formula(I).

Compounds of formula (I), alone or in blends, prove to be compoundsconcerning which the work of the inventors has shown that they arevolatile within a hydrocarbon binder of the bitumen type, and that theytherefore produce an effect similar to fluxants of petroleum origin, butwithout the problems of their environmental impact and of toxicity forthe handler.

In addition, compounds of formula (I), before being volatilised, producenot only a one-off reduction of the viscosity of the binder, but inaddition a wettability of the solid mineral particles by the binder ofthe same order as that of the best fluxant agents currently in use.

The compound of formula (I) as it is used according to the invention isnot used only to reduce the viscosity of the hydrocarbon binder butalso, more specifically, to produce a satisfactory wettability of thesolid mineral particles by the composition including the binder. To thisend, the compound of formula (I) is present in the bituminouscomposition for the whole or a part of the period of time during whichthe composition is brought into contact with the solid mineralparticles. In practice the compound of formula (I) can in particular beadded to the composition including the hydrocarbon binder according toone and/or other of the following 3 compatible variants:

-   -   variant 1: the compound of formula (I) is added at least partly        (if variant 2 and/or 3 is also used), or wholly (otherwise), to        the composition including the hydrocarbon binder; the        composition including the compound of formula (I) is then        brought into contact with the solid mineral particles before        complete evaporation of the compound of formula (I) outside the        composition (in other words the said compound of formula (I) is        still present, at least in part, in the composition when it is        brought into contact with the solid mineral particles,        preferably in a sufficient quantity in the composition for it to        act as a fluxant);    -   and/or    -   variant 2: the compound of formula (I) is added at least in part        (if variant 1 and/or 3 is also used), or wholly (otherwise), at        the same time as the solid mineral particles, to the composition        including the hydrocarbon binder    -   and/or    -   variant 3: the compound of formula (I) is added at least in part        (if variant 1 and/or 2 is also used), or wholly (otherwise), to        a pre-blend containing the solid mineral particles, and the        composition including the hydrocarbon binder

It should be noted that when variant 2 and/or 3 is used it can certainlybe envisaged to use, in a prior step (E0), compounds of formula (I) asfluxants in the binder-based composition (for example to manufacture acomposition of the bitumen emulsion type), and then to leave thecompounds of formula (I) used to evaporate completely. In this case, toimplement variant 2 or 3, compounds of formula (I), identical ordifferent to those used in the prior step (E0), will be introducedjointly and/or after the composition is blended with the solid mineralparticles.

The compounds of formula (I) according to the invention enable theviscosity of the hydrocarbon binder to which they are added to bereduced, whilst guaranteeing satisfactory wettability of the solidmineral particles by the composition including the binder.

Advantageously, the compounds of formula (I) according to the inventionalso enable a binder to be obtained which is effective afterstabilisation (this effectiveness can be ascertained by means ofpenetrability results, ring and ball temperature results, and possiblyFraass brittle point results)

Compounds of formula (I) according to the invention preferably enable areduction of the viscosity of the hydrocarbon binder when it is used,without affecting its properties and its ability to wet the solidmineral particles.

In one variant of the invention the composition also includes a compoundsatisfying formula (II)

R¹—X—R—Y—R²  (II)

-   -   where:    -   R¹ and R², which can be identical or different, are hydrocarbon        chains, linear or branched, at C₁-C₁₁, and preferably at C₁-C₉;        and where at least one of R¹, R² is a methyl radical    -   —X— and —Y—, —R— are as defined for formula (I).

According to the invention, it is possible to use a single compound offormula (II) or alternatively a blend of several compounds of formula(II).

The compounds of formula (II), alone or as part of blends, prove to becompounds concerning which the inventors' work has shown that they arevolatile within a hydrocarbon binder of the bitumen type.

This compound of formula (II) will advantageously be able to beintroduced in a blend with the compound of formula (I), according to oneand/or other of the above-mentioned variants 1, 2 and/or 3 or duringstep (E0). More generally, a fluxant agent and/or one or more compoundsof formula (II) will be able to be added to the composition beforeand/or during and/or after (and preferably before and/or during) thesolid mineral particles are brought into contact with the composition,regardless of when the compound of formula (I) is introduced. Accordingto one particular implementation, at least a proportion of the compoundsof formula (I) and at least a proportion of the compounds of formula(II) are present simultaneously in the composition, preferably at leastduring a part of the time when the composition is in contact with thesolid mineral particles.

The ratio of the content by weight of composition of formula (I) tocontent of compound of formula (II) is advantageously higher than orequal to 1, more advantageously between 1 and 5, and even moreadvantageously between 1 and 3.

The definitions below will be adopted throughout the presentdescription:

Hydrocarbon Binder:

The term “hydrocarbon binder” is understood to mean any hydrocarbonbinder of fossil or plant origin which can be used for the production of“bituminous” products, where this hydrocarbon binder typically may ormay not be bitumen, and be pure or modified, in particular through theaddition of polymer(s).

The binder will be able to be a soft to hard binder, advantageously of agrade ranging from 10/20 to 160/220.

The hydrocarbon binder can be a bitumen, whether pure or modified bypolymers.

The “polymer” modifying the bitumen to which reference is made here canbe chosen from among the natural or synthetic polymers. This relates,for example, to a polymer of the family of elastomers, whether syntheticor natural, and, indicatively and non-restrictively:

-   -   the statistical copolymers, whether multi-sequence or star, of        styrene and of butadiene or of isoprene in all proportions (in        particular block copolymers of styrene-butadiene-styrene (SBS),        styrene-butadiene (SB, SBR for styrene-butadiene rubber), of        styrene-isoprene-styrene (SIS)) or the copolymers of the same        chemical family (isoprene, natural rubber, etc.), possibly        cross-linked in situ,    -   the copolymers of vinyl and ethylene acetate, in all        proportions,        -   the copolymers of ethylene and of esters of acrylic or            methacrylic acid or of maleic anhydride, the copolymers and            terpolymers of ethylene and of glycidyl methacrylate) and            polyolefins.

The polymer modifying the bitumen can be chosen from among recoveredpolymers, for example “fine rubber powders”, or other rubber-basedcompositions reduced into pieces or powder, for example obtained fromworn tyres or other polymer-based waste (wires, packaging, agriculturalwaste, etc.) or alternatively all other polymers commonly used to modifybitumens, such as those cited in the Technical Guide written by theInternational Road Association (AIPCR) and published by LaboratoireCentral des Ponts et Chaussées [Central Bridges and Roads Laboratory]“Use of Modified Bituminous Binders, Special Bitumens and Bitumens withAdditives in Road Pavements” (Paris, LCPC, 1999), together with allblends in all proportions of these polymers.

The composition including the binder can be in the form of an anhydrousbinder or in the form of an emulsion (typically a bitumen emulsion).

The emulsion is a dispersion of the binder (bitumen, synthetic binder orplant binder) in a continuous phase, typically in an aqueous phase, forexample water. A surfactant agent can be added to the emulsion, which inparticular enables it to be stabilised.

During the manufacture of an emulsion the binder is dispersed in finedroplets in the water, for example by a mechanical action. Adding asurfactant agent forms a protective film around the droplets, preventingthem from coagulating, and thus enabling the blend to be kept stable,and enabling it to be stored for a certain period. The quantity and typeof surfactant agent added to the blend determine the stability of theemulsion when stored, and influence the curing time when it is laid. Thesurfactant agent can be positively charged, negatively charged,amphoteric or non-ionic.

The surfactant agent is advantageously of petroleum, plant or animalorigin, and blends of them (for example, the surfactant agent can be ofplant and petroleum origin). The surfactant agent can be an alkalinesoap of fatty acids: sodium or potassium salts of an organic acid (forexample resin). The emulsion is then anionic. The surfactant agent canbe an acidic soap, which is generally obtained by action of hydrochloricacid on one or two amines. The emulsion is then cationic. Among thesurfactants which are effective for road construction applications onecan cite: the surfactants sold by Akzo NOBEL (Redicote® E9, Redicote® EM44, Redicote® EM 76), the surfactants sold by CECA (Dinoram® S, Polyram®S, Polyram® L 80) and the surfactants sold by Meadwestvaco (Indulin®R33, Indulin® R66, Indulin® W5). One or more of these surfactants can beused, alone or in blends.

The emulsion can contain synthetic or natural latex. The term “latex” isunderstood to mean a dispersion of polymer (polyisoprene, SBS, SB, SBR,acrylic polymers, etc.) whether or not cross-linked, in aqueous phase.This latex is incorporated in the aqueous phase before emulsification orin the production line during manufacture of the emulsion, oralternatively after the emulsion has been manufactured.

The composition including the binder can take the form, wholly orpartly, of a foam typically obtained using a process of injecting aquantity of water, and possibly air, in the binder inlet, where thewater is pure or or can include additives enabling the adhesive force orrheological properties of the binder to be modified.

Whatever its form, the composition including the binder, typicallywithin the binder, additives commonly used in the road constructionfield, such as compositions based on powdered rubber (“fine rubberpowders”), plant waxes or waxes of petrochemical origin, adhesionagents.

Solid Mineral Particles

The term “solid mineral particles” is understood to mean, in the presentdescription, all solid particles which can be used to produce bituminousproducts, in particular for road construction, including in particularnatural mineral aggregates (chippings, sand, fines) derived fromquarries or gravel pits, recycling products such as asphalt mixaggregates resulting from the recycling of materials recovered whenroads are repaired, together with surpluses of coating plants,manufacturing scrap, “shingles” (derived from the recycling of roofmembranes), aggregates derived from the recycling of road materialsincluding concretes, slags, in particular scoria, schists, in particularbauxite or corumdum, fine rubber powders derived from the recycling oftyres in particular, artificial aggregates of all origins, derived forexample from clinkers from the incineration of household waste (MIOM),together with their blends in all proportions.

Natural mineral aggregates include:

-   -   elements smaller than 0.063 mm (filler or fines)    -   sand, the grains of which are between 0.063 mm and 2 mm in size;    -   chippings        -   of between 2 mm and 6 mm in size;        -   larger than 6 mm;

The size of the mineral aggregates is measured by the tests described instandard NF EN 933-2 (version of May 1996).

The term “asphalt mix aggregates” is understood to mean asphalt mixes(blend of aggregates and bituminous binders) derived from milling oflayers of asphalt mix, crushing of plates extracted from highways madefrom asphalt mixes, pieces of plates of asphalt mixes, asphalt mix wasteor surpluses from production of asphalt mixes (production surpluses arematerials which are coated or partially coated in the plant produced inthe transitional manufacturing phases). The size of these elements andthe other recycling products can be as as large as 31.5 mm.

The “solid mineral particles” are also designated by the terms “0/Dmineral fraction”. This 0/D mineral fraction can be separated into twogranulometries: the 0/d mineral fraction and the d/D mineral fraction.

The finest elements (the 0/d mineral fraction) will be those within therange 0 to a maximum diameter which can be set at between 2 and 6 mm(0/2 to 0/6), and advantageously between 2 and 4 mm. The other elements(minimum diameter greater than 2, 3, 4, 5 or 6 mm; and approximately ashigh as 31.5 mm) constitute the d/D mineral fraction.

Compound of Formula (I)

In the invention a compound, or blend of compounds, is used whichsatisfies formula (I)

R¹—X—R—Y—R²  (I)

-   -   where:    -   R¹ and R², which can be identical or different, are hydrocarbon        chains, linear or branched, at C₂-C₁₁, and preferably at C₂-C₉;    -   each of —X— and —Y—, which can be identical or different, is an        —O—(C═O)— group; —(C═O)—O—; —NR′—(C═O)—, where R′ represents a        hydrocarbon atom or an alkyl radical at C₁-C₄, or (C═O)—NR′—,        where R′ represents a hydrocarbon atom or an alkyl radical at        C₁-C₄,    -   the —R— group is a divalent hydrocarbon chain, at C₁-C₁₀, linear        or branched, and possibly interrupted by one or more oxygen        atom(s)

It should be noted that, according to a variant of the invention, thecompound of formula (I) may take the form of a blend comprising variouscompounds of formula (I). In the application, unless there is anexplicit mention of the presence of at least two compounds, “one”compound can designate a single compound satisfying formula (I) or ablend or an association of several compounds satisfying formula (I).

In the compounds of formula (I) used according to the invention, thetotal number of carbon atoms is preferably between 7 and 16. Accordingto one implementation the total number of carbon atoms is higher than orequal to 8, or higher than or equal to 9. According to oneimplementation, the total number of carbon atoms is 8, 9 or 10.According to one particular implementation, the number of carbon atomsis greater than or equal to 10, for example 11, and in particulargreater than or equal to 12. In addition, it is generally preferred thatthe total number of carbon atoms is fewer than or equal to 15, forexample fewer than or equal to 14. Thus, for example, the total numberof carbon atoms can be between 8 and 15, for example between 8 and 12 orbetween 10 and 15 or between 10 and 12 or between 12 and 14.

The total number of carbon atoms defined in the previous paragraph isvalid in particular when groups R, R¹ and R² are saturated groups,linear or branched, and in particular when these are saturated andbranched groups.

When compounds of formula (I) have linear chains, groups R¹ and R² aretypically saturated groups, generally identical, and containing 2 to 5carbon atoms, and advantageously 2, 3 or 4 carbon atoms. In this case,saturated group R generally contains 1 to 8 carbon atoms, for examplebetween 2 and 7, in particular between 2 and 6, with a total number ofcarbon atoms in the compound of formula (I) which can be between 8 and16, in particular between 10 and 16, for example between 8 and 12 orbetween 10 and 12 or between 12 and 14.

Compounds of formula (I) also have a molecular mass of between 170g/mole and 280 g/mole, more advantageously of between 180 g/mole and 280g/mole, more advantageously of between 190 g/mole and 275 g/mole, evenmore advantageously of between 200 g/mole and 265 g/mole or moreadvantageously of between 170 g/mole and 275 g/mole, and even moreadvantageously of between 170 g/mole and 265 g/mole.

Compounds of formula (I) prove to be volatile in most hydrocarbonbinders, and in particular in bitumen, meaning that over time they willevaporate from the bituminous compositions containing them, thusallowing cohesion increase of the bituminous products based on the saidbituminous compositions.

R′ advantageously represents a hydrogen atom or a methyl group or anethyl group.

Groups R¹ and R², which can be identical or different, advantageouslyrepresent an alkyl, aryl, alkyaryl or arylalkyl group, linear orbranched, whether or not cyclic, whether saturated or unsaturated, andusually saturated, at C₂-C₁₁, and typically at C₂-C₉.

Groups R¹ and R², which can be identical or different, can in particularbe chosen from among the ethyl, n-propyl, isopropyl, benzyl, phenyl,n-butyl, isobutyl, n-pentyl, isoamyl, cyclohexyl, hexyl, n-hexyl,heptyl, isooctyl, 2-ethylhexyl or 2-propylhexyl groups.

R¹ and R² each advantageously contains 2 to 5 carbon atoms, for example2 carbon atoms or 3 to 5 carbon atoms. Typically (in particular forreasons of ease of synthesis) R¹ and R² are identical and are chosenfrom among the ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentylor isoamyl groups, and in particular from among the ethyl or isobutylgroups.

The R group advantageously represents an alkanediyl radical at C₁-C₁₀,linear or branched, an alkenediyl radical at C₂-C₁₀, linear or branched,or indeed an alkoxylated chain, in particular an ethoxylated and/orpropoxylated chain, at C₂-C₁₀.

One can use as compounds of formula (I) compounds in which R is asdefined in one of the following implementations, or a blend ofcompound(s) according to these implementations:

-   -   Implementation 1: R is a radical of formula —(CH₂)_(r)—, where r        is an average number of between 2 and 8 inclusive. In        particular, R is a radical of formula —(CH₂)_(r)—, where r is an        average number of between 2 and 4 inclusive.

R is preferably chosen such that the compound can be a blend of adipatederivative (r=4), glutarate derivative (r=3), and succinate derivative(r=2).

-   -   Implementation 2: R is a branched alkanediyl radical at C₃-C₁₀.        R can in particular be a group at C₃, C₄, C₅, C₆, C₇, C₈, C₉, or        a blend. This is preferably a group at C₄.

Group R is preferably chosen from among the following groups:

-   -   the R_(MG) group of formula —CH(CH₃)—CH₂—CH₂—,    -   the R_(ES) group of formula —CH(C₂H₅)—CH₂—, and    -   their blends.

Such blends, together with appropriate methods for obtaining them, aredescribed in particular in documents WO 2007/101929; WO 2007/141404; WO2008/009792; WO 2008/062058.

-   -   Implementation 3: R is an alkenediyl radical, linear or        branched, at C₂-C₈, and advantageously at C₂-C₄.

Group R is preferably chosen from among the following groups:

-   -   the group of formula —CH═CH—, the double link being of        configuration Z    -   the group of formula —CH═CH—, the double link being of        configuration E    -   the group of formula —CH(CH₂)—CH₂—, and    -   their blends.    -   Implementation 4: R is a radical -(OE/OP)_(n)- where OE/OP are        alkoxy groups, preferably chosen from among the ethoxy and        propoxy groups and the ethoxy/propoxy blends, and n is an        average number of between 1 and 5 inclusive, and with a total        number of carbon atoms of 10 in group R.

In particular in the above-mentioned implementations 1 to 4, X and Y areadvantageously esters, and preferably esters of diacids (—X—=—O—(C═O)—;and Y=—(C═O)—O—) or esters of diols (—X—=—(C═O)—O— and Y=—O—(C═O)—)

Advantageously,

-   -   R¹ and R² are identical or different, and are each chosen from        among the ethyl, n-propyl, isopropyl, n-butyl, isobutyl,        n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl and        2-propylhexyl groups; in particular ethyl or isobutyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols        (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        diesters of glutarate (r=3), and diesters of succinate (r=2).

In one implementation of the invention the compound (I) used in thepresent invention is chosen from among diisobutyl adipate, diisobutylglutarate or diisobutyl succinate, and their blends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 5 to 29% by weight of diisobutyladipate (typically measured by Gas Phase Chromatography), 50 to 72% byweight of diisobutyl glutarate, and 10 to 32% by weight of diisobutylsuccinate.

The solvent sold by Solvay named Rhodiasolv® DIB can be used as compound(I).

In another implementation of the invention compound (I) used in thepresent invention is chosen from among diethyl adipate, diethylglutarate or diethyl succinate, and their blends.

A suitable blend can, for example, include, by weight relative to thetotal weight of the blend, a blend of 4 to 26% by weight of diethyladipate (typically measured by Gas Phase Chromatography), 52 to 77% byweight of diethyl glutarate, and 12 to 32% by weight of diethylsuccinate.

The solvent sold by Solvay named INNROAD® Protect can be used ascompound (I).

In yet another particular implementation of the invention compound (I)used in the present invention is chosen from among diisopropyl adipate,diisopropyl glutarate or diisopropyl succinate, and their blends.

A suitable blend, used in the examples and designated in the presentdescription by “DIP”, includes, by weight relative to the total weightof the blend, a blend of 5 to 29% by weight of diisopropyl adipate(typically measured by Gas Phase Chromatography), 50 to 72% by weight ofdiisopropyl glutarate, and 10 to 32% by weight of diisopropyl succinate.

In yet another possible implementation compound (I) used in the presentinvention is chosen from among diisoamyl adipate, diisoamyl glutarate ordiisoamyl succinate, and their blends.

A suitable blend, used in the examples and designated in the presentdescription by “DIA”, includes, by weight relative to the total weightof the blend, a blend of 5 to 29% by weight of diisoamyl adipate(typically measured by Gas Phase Chromatography), 50 to 72% by weight ofdiisoamyl glutarate, and 10 to 32% by weight of diisoamyl succinate.

A Compound of Formula (II)

A compound satisfying formula (II) can be used in the invention

R¹—X—R—Y—R²  (II)

-   -   where:    -   R¹ and R², which can be identical or different, are hydrocarbon        chains, linear or branched, at C₁-C₁₂, and preferably at C₁-C₁₀;        and where at least one of R¹, R² is a methyl radical    -   —X— and —Y—, —R— are as defined for formula (I).

It should be noted that according to a variant of the invention thecompound of formula (II) can take the form of a blend of variouscompounds of formula (II). In the application, unless there is anexplicit mention of the presence of two compounds, “one” compound canrefer to a single compound satisfying formula (II) or a blend of anassociation of several compounds satisfying formula (II).

Compounds of formula (II) advantageously have a molecular mass ofbetween 130 g/mole and 290 g/mole, more advantageously of between 140g/mole and 250 g/mole, and yet more advantageously of between 150 g/moleand 200 g/mole.

In compounds of formula (II) used according to the invention, the totalnumber of carbon atoms is preferably between 5 and 12. According to oneimplementation the total number of carbon atoms is higher than or equalto 6. In addition, it is generally preferred that the total number ofcarbon atoms is fewer than or equal to 11, for example fewer than orequal to 10. Thus, for example, the total number of carbon atoms can bebetween 6 and 11, for example between 6 and 8.

The total number of carbon atoms defined in the previous paragraph isvalid in particular when groups R, R¹ and R² are saturated groups,linear or branched,

-   -   —X— and —Y—, —R— are as defined for formula (I), including the        various variants.

Groups R¹ and R², which can be identical or different, advantageouslyrepresent an alkyl, aryl, alkyaryl or arylalkyl group, linear orbranched, whether or not cyclic, whether saturated or unsaturated, andusually saturated, at C₁-C₁, and typically at C₁-C₉. At least one of R¹,R² is a methyl radical.

Groups R¹ and R², which can be identical or different, can in particularbe chosen from among the methyl, ethyl, n-propyl, isopropyl, benzyl,phenyl, n-butyl, isobutyl, n-pentyl, isoamyl, cyclohexyl, hexyl,n-hexyl, heptyl, isooctyl, 2-ethylhexyl, or 2-propylhexyl groups. Atleast one of R¹, R² is a methyl radical.

Advantageously, R¹, R² both represent a methyl radical.

A compound of formula (II) according to the invention can, for example,be chosen from among dimethyl adipate, dimethyl glutarate, dimethylsuccinate, and their blends.

A suitable blend can, for example, include, by weight relative to thetotal weight of the blend, a blend of dimethyl adipate (for example 4 to22% by weight, by Gas Phase Chromatography), dimethyl glutarate (forexample 55 to 77% by weight), and dimethyl succinate (for example 12 to32% by weight).

The solvent sold by Solvay named Rhodiasolv® RPDE or the solvent sold bySolvay named INNROAD®Boost can be used as compound (II).

Another possible compound of formula (II), which can be used alone or ina blend with the previous one, is a compound for which R¹, R² bothrepresent a methyl radical and group R is chosen from among thefollowing groups:

-   -   the R_(MG) group of formula —CH(CH₃)—CH₂—CH₂—,    -   the R_(ES) group of formula —CH(C₂H₅)—CH₂—, and    -   their blends.    -   —X— and —Y— are advantageously esters, preferably esters of        diacids        (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols        (—X—=—(C═O)—O— and —Y—=—O—(C═O)—).

The solvent sold by Solvay named Rhodiasolv® IRIS can be used ascompound (II).

Bituminous Products

The term “bituminous product”, in the present invention, is understoodto mean a product based on a hydrocarbon binder and solid mineralparticles. One can in particular cite dressings, emulsion asphalt mixes,storable asphalt mixes, hot mixes, and warm mixes with controlledworkability which are described in greater detail below.

Bituminous products can contain high volumes (ranging from 0% to 100% byweight, advantageously from 20% to 50% by weight, relative to the totalweight) of recycling products (aggregates of asphalt product, asphaltmix aggregates).

Dressings

A surface dressing, within the meaning of the present description,refers to a layer consisting of superposed layers of a hydrocarbonbinder and of solid mineral particles. It is typically obtained byspraying a hydrocarbon binder and then by spreading solid mineralparticles on this binder, in one or more layers. The product is thencompacted. A surface dressing requires not only a binder which issufficiently fluid to be able to be sprayed, but also a binder whichenables satisfactory bonding of the solid mineral particles on to thesupport.

The fluxant added to the binder must thus enable it to be softenedwithout impairing the wetting of the solid mineral particles by thebinder. The fluxant must also enable the binder to be softened when itis being sprayed, but when it has been sprayed the binder must hardenrapidly, in order also to meet the criterion of cohesion increase. Ifthe binder does not correctly wet the solid mineral particles theadhesion of this binder on to these particles will not be satisfactory,or unacceptable.

The binder-solid mineral particles affinity is determined by thepossibility of wetting of the solid mineral particles by the binder,which can be assessed by means of the test for determining thebinders-aggregates adhesive force by measuring the Vialit cohesion (NFEN 12272-3, 2003 Jul. 1).

It has been discovered that compounds of formula (I) enable the binderto be fluxed effectively, with satisfactory cohesion increase, withoutimpairing the binder-solid mineral particles affinity.

Compound(s) of formula (I) are advantageously added in their entirety tothe composition including the hydrocarbon binder and then thecomposition including the hydrocarbon binder and the compound(s) offormula (I) is sprayed on the solid mineral particles before thecompound of formula (I) evaporates completely out of the composition. Inother words, the said compound of formula (I) is still present at leastin part when the fluxed binder and the solid mineral particles arebrought into contact, preferably in a sufficient quantity in thecomposition to allow satisfactory adhesion of the binder to the solidmineral particles.

In an implementation suitable for dressings, in formula (I)

-   -   R¹ and R² are identical, and each is chosen from among the        ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl,        isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl or 2-propylhexyl        groups, and in particular from the isobutyl group;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols        (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        of diesters of glutarate (r=3), and of diesters of succinate        (r=2).

In an advantageous implementation of the invention, compound (I) used ina dressing is diisobutyl adipate, diisobutyl glutarate or diisobutylsuccinate, and their blends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 5 to 29% by weight of diisobutyladipate (typically measured by Gas Phase Chromatography), 50 to 72% byweight of diisobutyl glutarate, and 10 to 32% by weight of diisobutylsuccinate.

The solvent sold by Solvay named Rhodiasolv® DIB can be used as compound(I).

In another advantageous implementation of the invention compound (I)used in the present invention is chosen from among diethyl adipate,diethyl glutarate or diethyl succinate, and their blends.

A suitable blend can, for example, include, by weight relative to thetotal weight of the blend, a blend of 4 to 26% by weight of diethyladipate (typically measured by Gas Phase Chromatography), 52 to 77% byweight of diethyl glutarate, and 12 to 32% by weight of diethylsuccinate.

The solvent sold by Solvay named INNROAD® Protect can be used ascompound (I).

The solid mineral particles used in a dressing advantageously belong tothe following granular classes (d/D): 4/6.3, 6.3/10, 10/14.

The total hydrocarbon binder content in a dressing will be modifieddepending on the structure of the dressing (single- or twin-layer, typeof chippings), on the nature of the binder and on the dimension of theaggregates, following for example the recommendations of the document“Wear surface dressings —Technical Guide, May 1995”.

The hydrocarbon binder used for the manufacture of a dressing can be apure bitumen or one modified by polymers, as described above.

The hydrocarbon binder used for the manufacture of a dressing can be inthe form of an anhydrous binder, or in the form of an emulsion binder.

In one implementation the hydrocarbon binder is used in the form of ananhydrous binder when manufacturing the dressing.

In this implementation the hydrocarbon binder advantageously includes,relative to the total weight of the hydrocarbon binder, 3% to 18% byweight of the said compound of formula (I).

In this implementation the dressing is advantageously used at atemperature of less than or equal to 200° C., for example ranging from120° C. to 180° C. or ranging from 130° C. to 160° C.

In another implementation the hydrocarbon binder is an emulsion binder.

In this implementation the hydrocarbon binder advantageously includes,relative to the total weight of the hydrocarbon binder, 0.1 to 10% byweight of the said compound of formula (I), more advantageously 0.5 to8% by weight, and yet more advantageously 1 to 6% by weight.

In this implementation the dressing is advantageously used at atemperature of less than or equal to 40° C., for example ranging from 5°C. to 40° C. or ranging from 15° C. to 35° C.

Bituminous Concretes with Emulsion

Bituminous concretes with emulsion, also called emulsion asphalt mixes,are hydrocarbon asphalt mixes produced cold from aggregates and anemulsified hydrocarbon binder. The aggregates can be used without priordrying and heating, or be subject to partial, hot pre-coating. It cansometimes be necessary to heat the product after it is manufactured,when it is used.

This technique, called the “cold” technique, has in environmental termsthe major advantage that it does not produce smoke emissions, whichreduces the disturbance for workers and persons in the vicinity.Bituminous concretes with emulsion consist of a blend of solid mineralparticles including aggregates, bitumen emulsion (whether or notmodified), and additives.

However, the quality of the coating can be mediocre, and a phenomenon ofravelling can be seen: poor distribution of the bitumen film over theentire granular fraction, particularly if the fluxant or fluidifiercontent is high. The more fines the granular fraction contains thepoorer the distribution of the binder will be over the granular fraction(mainly on the large elements).

To remedy or restrict these problems of loss of compactability and ofpoor distribution of the bitumen film over the entire granular fraction,the step of blending of the granular fractions and of the binder, andpossibly of the fluxant agent, can be sequenced. These sequenced methodsimply more steps, and are thus less economic.

It has now been discovered that compounds of formula (I) enablebituminous concretes with emulsion to be fluxed effectively. Compoundsof formula (I) also assist with compacting. The invention can alsoenable the use of sequenced methods and/or heating to be avoided.

The compound(s) of formula (I) is/are advantageously added to thecomposition including the hydrocarbon binder according to one and/orother of the 3 variants described above on pages 4 and 5, and thusbefore and/or during and/or after the binder and the solid mineralparticles are brought into contact. The compound(s) of formula (I)is/are introduced at the latest before the bituminous concrete withemulsion is used, and is/are present at least in part in the compositionincluding the binder and the solid mineral particles to allowsatisfactory adhesion.

In an implementation suitable for bituminous concretes, the compound(s)of formula (I) is/are introduced into the composition including theemulsion binder, and the said composition is then brought into contactwith the solid mineral particles (variant 1).

In another implementation suitable for bituminous concretes, thecompound(s) of formula (I) is/are introduced at least partly at the sametime as the solid mineral particles into the composition including thehydrocarbon binder (variant 2).

In another implementation suitable for bituminous concretes, aproportion or all the compound(s) of formula (I) is/are introduced in apre-blend based on emulsion binder and solid mineral particles (variant3). The resulting composition still includes a sufficient quantity ofcompound of formula (I) for the bituminous concrete with emulsion to beused.

In yet another implementation suitable for bituminous concretes, informula (I)

-   -   R¹ and R² are identical, and each is chosen from among the        ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl,        isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl or 2-propylhexyl        groups, and in particular from the isobutyl group;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        of diesters of glutarate (r=3), and of diesters of succinate        (r=2).

Advantageously, compound (I) used for bituminous concretes with emulsionis diisobutyl adipate, diisobutyl glutarate or diisobutyl succinate, andtheir blends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 5 to 29% by weight of diisobutyladipate (typically measured by Gas Phase Chromatography), 50 to 72% byweight of diisobutyl glutarate, and 10 to 32% by weight of diisobutylsuccinate.

The solvent sold by Solvay named Rhodiasolv® DIB can be used as compound(I).

Compounds of formula (I), chosen in particular from among diethyladipate, diethyl glutarate or diethyl succinate, and their blends, allowsatisfactory compacting of the bituminous concrete with emulsion.

A suitable blend of compounds of formula (I) can, for example, include,by weight in relation to the total weight of the blend, a blend of 4 to26% by weight of diethyl adipate (typically measured by Gas PhaseChromatography), 52 to 77% by weight of diethyl glutarate, and 12 to 32%by weight of diethyl succinate.

The solvent sold by Solvay named INNROAD® Protect can be used ascompound (I).

Advantageously, for a bituminous concrete with emulsion, a compound offormula (II) of the above-mentioned type is also added.

In a first implementation suitable for bituminous concretes withemulsion, in formula (II):

-   -   R¹ and R² are identical and are each methyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        of diesters of glutarate (r=3), and of diesters of succinate        (r=2).

Advantageously, compound (I) used for bituminous concretes with emulsionis dimethyl adipate, dimethyl glutarate or dimethyl succinate, and theirblends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 4 to 22% by weight of dimethyladipate (typically measured by Gas Phase Chromatography), 55 to 77% byweight of dimethyl glutarate, and 12 to 32% by weight of dimethylsuccinate.

The solvent sold by Solvay named Rhodiasolv® RPDE or the solvent sold bySolvay named INNROAD®Boost can be used as compound (II).

In a second implementation suitable for bituminous concretes withemulsion, in formula (II):

-   -   R¹ and R² are identical and are each methyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is chosen from among the following groups:        -   the R_(MG) group of formula —CH(CH₃)—CH₂—CH₂—,        -   the R_(E)s group of formula —CH(C₂H₅)—CH₂—, and        -   their blends.

In particular, the product sold by the company Solvay named Rhodiasolv®IRIS can be used as a compound of formula (II) for bituminous concreteswith emulsion.

Solid mineral particles for bituminous concretes with emulsionadvantageously include:

-   -   elements smaller than 0.063 mm (filler or fines)    -   sand, the grains of which are between 0.063 mm and 2 mm in size;    -   chippings between 2 mm and 6, 10 or 14 mm in size.

The hydrocarbon binder used for the synthesis of bituminous concreteswith emulsion is in the form of emulsion binder. The total hydrocarbonbinder content in the said emulsion is typically 2 to 8 pph (parts perhundred by weight), advantageously 3 to 7 pph, more advantageously 3.5to 5.5 pph, relative to the weight of the solid mineral particles. Thisbinder content is the quantity of binder introduced as such (contributedbinder), plus the quantity of binder recovered from asphalt mixaggregates forming part of the solid mineral fraction.

The hydrocarbon binder in an emulsion used to manufacture a bituminousconcrete with emulsion advantageously includes, relative to the totalweight of hydrocarbon binder, 1 to 25% by weight of the said compound offormula (I), more advantageously 2 to 15% by weight, yet moreadvantageously 2 to 10% by weight, and yet more advantageously 3 to 10%by weight. These contents are calculated whether the compound of formula(I) is actually added to the binder before it is brought into contactwith the solid mineral particles, or whether it is added to thecomposition including the binder and the solid mineral particles.

The hydrocarbon binder in an emulsion used for the manufacture of abituminous concrete with emulsion can, possibly, include a compound offormula (II), advantageously 0.1 to 5% by weight of the said compound offormula (II), compared to the total weight of the hydrocarbon binder.These contents are calculated whether the compound of formula (II) isactually added to the binder before it is brought into contact with thesolid mineral particles, or whether it is added to the compositionincluding the binder and the solid mineral particles.

The bituminous concretes obtained according to the invention withemulsion can be used to manufacture storable asphalt mixes.

In this implementation the hydrocarbon binder advantageously includes,relative to the total weight of the hydrocarbon binder, 10 to 30% byweight of the said compound of formula (I), more advantageously 15 to25% by weight, and yet more advantageously 17 to 22% by weight.

Cold Mix Bituminous Materials

Cold mix bituminous materials are surface course asphalt mixesconsisting of undried aggregates coated with bitumen emulsion and pouredin place continuously using a specific plant engine.

After the emulsion is used and broken a very thin layer of this cold mixcoating (generally 6 to 13 mm thickness per layer) must reach its finalconsistency (cohesion increase) very rapidly. The two essentialparameters governing the formulation, manufacture and use of cold mixbituminous materials are:

-   -   the workability of the aggregates/emulsion blend: optimisation        of the proportions of the various constituents (water,        additives, formulation of the emulsion) to obtain a sufficient        period of use, and thus allow the aggregates to be blended with        the emulsion in the mixer.    -   the kinetics of “cohesion increase”: after application on the        highway the cold mix bituminous material must acquire cohesion        increase as rapidly as possible for re-opening to traffic. For        curing temperatures ranging from 7 to 40° C., a period of 30        minutes is considered as effective for those skilled in the art        to meet the strictest specifications.

It has been discovered that compounds of formula (I) enable cold mixbituminous materials to be fluxed effectively. In particular, compoundsof formula (I) enable the kinetics of cohesion increase of the cold mixbituminous material to be improved.

For a cold mix bituminous material the initially separated bitumendroplets give the system a fluid character and allow easy applicationusing machines which are specific for cold mix bituminous materials. Thesystem is then viscous. The characteristic period during which thisstate persists is called the workability period. In a subsequent periodthe bitumen droplets gradually coalesce. When all the bitumen dropletsare grouped together it is considered that the emulsion has broken(breaking time). The system is then viscoelastic. The systemsubsequently tends to contract so as to reduce the contact surfacebetween the water and the bitumen (cohesion period). This process adoptskinetics which will depend on the electrostatic repulsions between thedroplets and therefore on the nature of the bitumen and the emulsifier.The kinetics of the coalescence reaction between the bitumen dropletswill determine the speed of the cohesion increase of the cold mixbituminous material, which will be reflected by the material'ssensitivity, or lack thereof, to the curing conditions when freshlypoured Compounds of formula (I) advantageously enable the coalescence ofthe bitumen droplets to be facilitated.

In an implementation suitable for cold mix bituminous materials thecompound(s) of formula (I) is/are introduced into the compositionincluding the emulsion binder, and the said composition is then broughtinto contact with the solid mineral particles (variant 1).

In a first variant of the previous implementation, the compound(s) offormula (I) is/are introduced into the binder, and the binder is thenemulsified in a continuous aqueous phase.

In a second variant of the previous implementation, the compound(s) offormula (I) is/are introduced into the already emulsified binder

In another implementation suitable for cold mix bituminous materials,the compound(s) of formula (I) is/are added at the same time as thesolid mineral particles into the composition including the emulsifiedhydrocarbon binder (variant 2). It is possible to pre-blend thecompounds of formula (I) and the solid mineral particles.

In another implementation the previous two implementations are combined,and thus:

-   -   a proportion of the compound(s) of formula (I) is introduced        into the composition including the emulsion binder, according to        the first or second variant, and the said composition is then        brought into contact with solid mineral particles and    -   another proportion of the compound(s) of formula (I) is added at        the same time as the solid mineral particles to the composition        including the emulsified hydrocarbon binder and the previously        introduced portion of the compounds of formula (I).

In another implementation suitable for cold mix bituminous materials, aproportion or all the compound(s) of formula (I) is/are introduced in apre-blend based on emulsion binder and solid mineral particles (variant3), before the emulsion breaks.

In an implementation suitable for cold mix bituminous materials, informula (I)

-   -   R¹ and R² are identical, and each is chosen from among the        ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, isoamyl,        isobutyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl or        2-propylhexyl groups, and in particular from the isobutyl group;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        of diesters of glutarate (r=3), and of diesters of succinate        (r=2).

Advantageously, for cold mix bituminous materials, compound (I) used inthe present invention is diisobutyl adipate, diisobutyl glutarate ordiisobutyl succinate, and their blends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 5 to 29% by weight of diisobutyladipate (typically measured by Gas Phase Chromatography), 50 to 72% byweight of diisobutyl glutarate, and 10 to 32% by weight of diisobutylsuccinate.

The solvent sold by Solvay named Rhodiasolv® DIB can be used as compound(I).

It has been discovered, surprisingly, that the cohesion increase couldbe improved further when compound (I) used in the present invention ischosen from among diethyl adipate, diethyl glutarate or diethylsuccinate, and their blends.

A suitable blend can, for example, include, by weight relative to thetotal weight of the blend, a blend of 4 to 26% by weight of diethyladipate (typically measured by Gas Phase Chromatography), 52 to 77% byweight of diethyl glutarate, and 12 to 32% by weight of diethylsuccinate.

The solvent sold by Solvay named INNROAD® Protect can be used ascompound (I).

Advantageously, for a cold mix bituminous material, a compound offormula (II) is also added.

In a first implementation, in formula (II):

-   -   R¹ and R² are identical and are each methyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        diesters of glutarate (r=3), and diesters of succinate (r=2).

Advantageously, compound (II) used for cold mix bituminous materials isdimethyl adipate, dimethyl glutarate, dimethyl succinate, and theirblends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 4 to 22% by weight of dimethyladipate (typically measured by Gas Phase Chromatography), 55 to 77% byweight of dimethyl glutarate, and 12 to 32% by weight of dimethylsuccinate.

The solvent sold by Solvay named Rhodiasolv® RPDE or the solvent sold bySolvay named INNROAD®Boost can be used as compound (II).

In a second implementation suitable for cold mix bituminous materials,in formula (II):

-   -   R¹ and R² are identical and are each methyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is chosen from among the following groups:        -   the R_(M)G group of formula —CH(CH₃)—CH₂—CH₂—,        -   the R_(ES) group of formula —CH(C₂H₅)—CH₂—, and        -   their blends.

In particular, a compound of formula (II) suitable for cold mixbituminous materials is the product sold by Solvay named Rhodiasolv®IRIS.

The solid mineral particles used for cold mix bituminous materialsadvantageously include:

-   -   elements smaller than 0.063 mm (filler or fines)    -   sand, the grains of which are between 0.063 mm and 2 mm in size;        -   chippings, the elements of which are between 2 mm and 6, 10            or 14 mm in size.

The hydrocarbon binder used for the manufacture of cold mix bituminousmaterials is in the form of an emulsion binder.

In this emulsion the binder content advantageously varies from 50 to 75%by weight of binder, relative to the total weight of the emulsion, moreadvantageously from 55 to 70% by weight, and yet more advantageouslyfrom 60 to 65% by weight.

The hydrocarbon binder suitable for cold mix bituminous materialsadvantageously includes, relative to the total weight of the hydrocarbonbinder, 0.1 to 6% by weight of the said compound of formula (I), andmore advantageously 0.1 to 3% by weight of the said compound of formula(I). In a variant, the hydrocarbon binder includes less than 2% byweight of the said compound of formula (I), advantageously less than1.5% by weight, and yet more advantageously 0.1 to 1% by weight of thesaid compound of formula (I).

The hydrocarbon binder suitable for cold mix bituminous materialsadvantageously includes, relative to the total weight of the hydrocarbonbinder, 0.1 to 3% by weight of the said compound of formula (II), andmore advantageously 0.1 to 1% by weight of the said compound of formula(II).

Hot or Warm Mix Hydrocarbon Asphalt Mixes

Hot mix hydrocarbon asphalt mixes are obtained by hot mixing of theaggregates and of a binder. This binder can be a pure bitumen or amodified bitumen (for example, addition of polymer(s), fluxants ofpetroleum or plant origin), a pure or modified plant binder, or asynthetic binder of petroleum origin. The aggregates are heated,generally to a temperature of over 100° C.

Warm hydrocarbon asphalt mixes are asphalt mixes used at temperatures ofapproximately 30 to 50° C. below the temperatures used for hot mixhydrocarbon asphalt mixes.

It has been discovered that compounds of formula (I) enable hot or warmmix hydrocarbon asphalt mixes to be fluxed effectively, with asatisfactory cohesion increase, and satisfactory wettability of thesolid mineral particles.

The compound(s) of formula (I) is/are advantageously added to thecomposition including the hydrocarbon binder according to one and/orother of the 3 variants described above on pages 4 and 5, and thusbefore and/or during and/or after the binder and the solid mineralparticles are brought into contact. The compound(s) of formula (I)is/are introduced at the latest before the hot or warm mix hydrocarbonasphalt mixes are used, and is/are present at least in part in thecomposition including the binder and the solid mineral particles toallow satisfactory adhesion.

In a suitable implementation, the compound(s) of formula (I) is/areintroduced in the composition including the binder, and the saidcomposition is then brought into contact with solid mineral particles(variant 1).

In one implementation, suitable for hot or warm mix hydrocarbon asphaltmixes, in formula (I)

-   -   R¹ and R² are identical, and each is chosen from among the        ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl,        isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl or 2-propylhexyl        groups, and in particular from the isobutyl group;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        diesters of glutarate (r=3), and diesters of succinate (r=2).

Advantageously, compound (I) used in the present invention is diisobutyladipate, diisobutyl glutarate or diisobutyl succinate, and their blends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 5 to 29% by weight of diisobutyladipate (typically measured by Gas Phase Chromatography), 50 to 72% byweight of diisobutyl glutarate, and 10 to 32% by weight of diisobutylsuccinate.

The solvent sold by Solvay named Rhodiasolv® DIB can be used as compound(I).

Advantageously, compound (I) used in the present invention is chosenfrom among diethyl adipate, diethyl glutarate or diethyl succinate, andtheir blends.

A suitable blend can, for example, include, by weight relative to thetotal weight of the blend, a blend of 4 to 26% by weight of diethyladipate (typically measured by Gas Phase Chromatography), 52 to 77% byweight of diethyl glutarate, and 12 to 32% by weight of diethylsuccinate.

the solvent sold by solvay named INNROAD® Protect can be used ascompound (I).

Advantageously, for hot mix hydrocarbon asphalt mixes, a compound offormula (II) of the above-mentioned type is also added.

In a first implementation, suitable for hot mix hydrocarbon asphaltmixes, in formula (II):

-   -   R¹ and R² are identical and are each methyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols    -   (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is a radical of formula —(CH₂)_(r)—, where r is an average        number of between 2 and 4 inclusive. R is preferably chosen such        that the compound can be a blend of diesters of adipate (r=4),        diesters of glutarate (r=3), and diesters of succinate (r=2).

Advantageously, compound (II) used for cold mix bituminous materials isdimethyl adipate, dimethyl glutarate, dimethyl succinate, and theirblends.

A suitable blend can, for example, include, by weight in relation to thetotal weight of the blend, a blend of 4 to 22% by weight of dimethyladipate (typically measured by Gas Phase Chromatography), 55 to 77% byweight of dimethyl glutarate, and 12 to 32% by weight of dimethylsuccinate.

The solvent sold by Solvay named Rhodiasolv® RPDE or the solvent sold bySolvay named INNROAD®Boost can be used as compound (II).

In a second implementation, suitable for hot mix hydrocarbon asphaltmixes, in formula (II):

-   -   R¹ and R² are identical and are each methyl;    -   X and Y are advantageously esters, and preferably esters of        diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols        (—X—=—(C═O)—O— and —Y—=—O—(C═O)—)    -   R is chosen from among the following groups:        -   the R_(MG) group of formula —CH(CH₃)—CH₂—CH₂—,        -   the R_(ES) group of formula —CH(C₂H₅)—CH₂—, and        -   their blends.

In particular, the product sold by the company Solvay named Rhodiasolv®IRIS can be used as a compound of formula (II) for hot mix hydrocarbonasphalt mixes.

The solid mineral particles are as defined above, and advantageouslyinclude:

-   -   elements smaller than 0.063 mm (filler or fines)    -   sand, the grains of which are between 0.063 mm and 2 mm in size;        -   chippings, the elements of which are between 2 mm and 6, 10            or 14 mm in size.

The hydrocarbon binder is in the anhydrous form.

The total hydrocarbon binder content is 3 to 7 pph (parts per hundred byweight), more advantageously 3.5 to 6 pph, relative to the weight of thesolid mineral particles.

This binder content is the quantity of binder introduced as such(contributed binder), plus the quantity of binder recovered from asphaltmix aggregates forming part of the solid mineral fraction.

In the case of hot or warm hydrocarbon asphalt mixes the hydrocarbonbinder advantageously includes, relative to the total weight of thehydrocarbon binder, 1 to 30% by weight of the said compound of formula(I).

In the case of hot hydrocarbon asphalt mixes the hydrocarbon binder canalso advantageously include, relative to the total weight of thehydrocarbon binder, 1 to 30% by weight of the said compound of formula(II).

The fluxant content is adjusted according to the period betweenmanufacture and implementation.

When the hot or warm hydrocarbon asphalt mixes are used rapidly aftermanufacture, for example for the manufacture of surface courses, thehydrocarbon binder advantageously includes, relative to the total weightof the hydrocarbon binder, 0.1 to 6% by weight of the said compound offormula (I).

When the hot hydrocarbon asphalt mixes are used rapidly aftermanufacture, for example for the manufacture of surface courses, thehydrocarbon binder can also include, relative to the total weight of thehydrocarbon binder, 0.1 to 6% by weight of the said compound of formula(II).

These hot or warm hydrocarbon asphalt mixes can also be used for themanufacture of storable asphalt mixes.

In this implementation the hydrocarbon binder advantageously includes,relative to the total weight of the hydrocarbon binder, 15 to 30% byweight of the said compound of formula (I), more advantageously 15 to25% by weight, and yet more advantageously 17 to 22% by weight.

In this implementation compound (I) is advantageously chosen from amongdiethyl adipate, diethyl glutarate or diethyl succinate, and theirblends.

A suitable blend can, for example, include, by weight relative to thetotal weight of the blend, a blend of 4 to 26% by weight of diethyladipate (typically measured by Gas Phase Chromatography), 52 to 77% byweight of diethyl glutarate, and 12 to 32% by weight of diethylsuccinate.

The solvent sold by Solvay named INNROAD® Protect can be used ascompound (I).

In the case of hot hydrocarbon asphalt mixes the hydrocarbon binder canalso include, relative to the total weight of the hydrocarbon binder, 15to 30% by weight of the said compound of formula (II), moreadvantageously 15 to 25% by weight, and yet more advantageously 17 to22% by weight.

EXAMPLES Description and Test Methods:

-   -   Stabilisation of fluxed binders:        -   Anhydrous binders: This is a method for obtaining a thin            binder layer. Stabilisation is accomplished according to            standard NF EN 13074 1.2 (April 2011), leaving the fluxed            bitumen for 24 h at laboratory temperature and then            transferring it to a ventilated kiln for 24 h at 50° C., and            finally for 24 h at 80° C. to enable evaporation of the            fluxant.        -   Emulsion binders: This is a method for obtaining a thin            binder layer. Stabilisation is accomplished according to            standard NF EN 13074 1.2 (April 2011), leaving the bitumen            emulsion for 24 h at laboratory temperature and then            transferring it to a ventilated kiln for 24 h at 50° C., and            finally for 24 h at 80° C. to enable evaporation of the            water and possibly of a fluxant.    -   STV pseudo-viscosity:        -   Case of anhydrous binders: This is a method for measuring            the viscosity of a fluxed bitumen by determination of the            flow time of the product at 40° C. or 50° C. through an            aperture measuring 10 mm. STV pseudo-viscosity is measured            according to standard NF EN 12846-2 (April 2011).        -   Case of emulsion binders: This is a method for measuring the            viscosity of a bitumen emulsion by determination of the flow            time of the product at 40° C. through an aperture measuring            2 and/or 4 mm. STV pseudo-viscosity is measured according to            standard NF EN 12846-1 (April 2011).    -   Dynamic viscosity: TO BE COMPLETED        -   Anhydrous binder: The dynamic viscosity of a fluxed bitumen            is measured at approximately 140° C. (80° C. above the            softening point) using a rotational viscosimeter NF EN 13302            (April 2010)        -   Emulsion: The dynamic viscosity of a bitumen emulsion is            measured at 40° C. using a rotational viscosimeter NF EN            13302 (April 2010)    -   Penetrability: Penetrability is the consistency expressed as the        depth, in tenths of millimetres, corresponding to the vertical        penetration of a reference needle in a test sample of the        material, under prescribed conditions of temperature, load and        period of application of the load. The penetrability test is        conducted according to standard NF EN 1426 (June 2007). In the        examples the measurements were made at 25° C., for a load of 100        g and a period of 5 s. Penetrability can be measured from a        fluxed bitumen, a stabilised binder obtained from a fluxed        bitumen, or alternatively from a stabilised binder obtained from        a bitumen emulsion.    -   Ball-ring temperature: This is the temperature at which the        binder reaches a precise consistency under the reference        conditions of the test. Two horizontal discs of bitumen, moulded        in brass shouldered rings, are heated in a liquid bath (water)        stirred with a controlled rate of temperature rise (5° C./min.,        initial temperature of the bath of (5±1) ° C.), when each        supports a steel ball. The noted softening point must be equal        to the average of the temperatures at which both discs soften        sufficiently to enable each ball, coated in bituminous binder,        to descend by a height of (25.0±0.4) mm. The measurement is made        according to standard NF EN 1427 (June 2007). The ball-ring        temperature can be measured from a fluxed bitumen, a stabilised        binder obtained from a fluxed bitumen, or alternatively from a        stabilised binder obtained from a bitumen emulsion.    -   FRAASS brittle point: This test consists in measuring the        temperature at which cracks appear in a film spread on a blade        subjected to successive bending actions. The higher the FRAASS        point the more fragile is the bitumen. The measurement is made        according to standard NF EN 12593 (August 2015).    -   Mass loss after stabilisation: Mass loss after stabilisation is        measured according to the mass difference between the binder        deposited at the start of the stabilisation procedure and the        mass of binder actually measured after the step of stabilisation        (standard NF EN 13074 1.2, April 2011)    -   Evaporation curves (thermobalance): This is a measurement of the        mass loss of a fluxed bitumen as a function of time at a fixed        temperature of 85° C. The test is conducted using a        thermobalance and enables the evaporation kinetics of a fluxant        to be evaluated.    -   Adhesive force: This is a method for determining the        binder-aggregates adhesive force and the influence of additives        on the characteristics of this adhesive force (Standard NF EN        12272-3, July 2003). The quantity of binder required is heated        to the spreading temperature, and then applied uniformly on a        steel plate. The test is conducted at (5±1)° C. 100 calibrated        chippings are spread on the binder and then rolled flat. The        plate prepared in this manner is turned over and then placed on        a three-point support. A steel ball falls on the plate from a        height of 500 mm, three times in 10 s.    -   Homogeneity by sieving: This is a method for determining the        quantity of large particles of binder present in bitumen        emulsions. A known mass of bitumen emulsion is filtered, either        through a prepared sieve with an aperture size of 0.500 mm, or        through two prepared sieves, one with an aperture size of 0.500        mm and the other with an aperture size of 0.160 mm. The quantity        of binder found on each sieve is weighed after washing and        drying. (NF EN 1429—August 2013)    -   Storage stability by sieving: Storage stability is determined by        the quantity of binder (bitumen emulsion) retained on the sieve        with an aperture size of 0.500 mm after a defined storage period        (n days) (NF EN 1429—August 2013).    -   LASER granulometry: Laser granulometry enables the average size        of the bitumen droplets of an emulsion and their distribution to        be determined. This method also enables the surface specific        area of the bitumen droplets to be measured. (Internal test        method) Breaking index: The test consists in determining by        weighing the quantity of reference fines (Sikaïsol and/or        Forshammer) to be added under stirring at constant speed to the        bitumen emulsion in order to break this emulsion (NF EN        13075-1—December 2016)    -   Settling: This method enables the settling tendency of a bitumen        emulsion to be evaluated. The sample is left still for a certain        period in a stoppered, graduated test tube, after which time the        water contents of the upper and lower layers are determined in        accordance with EN 1428 or EN 1431. The settling tendency is        calculated using the difference between the two water contents.        (NF EN 12847—August 2009)    -   Adhesive force by a water immersion test according to standard        NF EN 13614 A—June 2011: The bitumen emulsion is blended        carefully with the selected aggregate under specified        conditions. To measure the effect of the water on the binder's        adhesion the blend is first cured, and then immersed in water        under specified conditions. The surface percentage of aggregate        covered with binder is assessed visually under specified        conditions.    -   The compactability of a bituminous concrete with emulsion is        determined by the compacting test using the gyratory shear        compactor (NF P 98-252—June 1999): Compacting is obtained by        kneading under low static compression with a cylinder of        hydrocarbon blend contained in a mould limited by discs, kept at        a fixed temperature. Compacting is obtained by the combination        of gyratory shearing and a resulting axial force applied by a        mechanical head. This method enables the change of percentage of        voids of the test specimen to be determined according to the        number of gyrations.    -   BBE module (NF EN 12697-26 Appendix C—June 2012): Before        measuring the modulus of rigidity, test specimens of bituminous        concrete with emulsion are prepared by press compacting at a        voids content value equivalent to the voids content measured        according to the Duriez test method 2, by removing 2%. The test        specimens are then subject to curing at 35° C. and 20%        hygrometry for 14 days. The modulus of rigidity is then measured        after 14 days by indirect traction on cylindrical test specimens        conditioned at 10° C. (IT-CY). The rise time, measured from the        start of the loading pulse, which is the time required for the        application of the load to change from the initial contact load        to the maximum value, must be 124±4 ms.    -   BBE workability: This test is conducted 4 hours after        manufacture of the BBE with a NYNAS workability meter. It        consists in measuring the force required by a mobile arm to        displace at constant speed approximately 10 kg of asphalt mix        contained in a mould designed for this purpose. The workability        of the asphalt mix is sufficient if the force is less than        approximately 200 Newton.

Description of the Tested Compounds:

The following compounds were tested:

-   -   Compounds of formula (I):

1. Rhodiasolv® DIB. This compound is named “DIB” in the followingtables.

2. INNROAD® protect. This compound is named “INNROAD® Protect” in thefollowing tables.

3. DIP as defined by the description, designated “DIP” in the followingtables.

4. DIA as defined by the description, referred to as “DIA” in thefollowing tables.

-   -   Compounds of formula (II):

1. Rhodiasolv® RPDE. This compound is named “RPDE” in the followingtables.

2. Rhodiasolv® IRIS. This compound is named “IRIS” in the followingtables.

The physico-chemical properties of these compounds are given in thefollowing table:

TABLE 1 Flash point Vapour in closed Density Boiling Mw pressure vesselat 20° C. range (g/mole) (Pa) (° C.) (g/cm³) (° C.) RPDE 159 9.4 991.0915 195-216 IRIS 174 6.3 98 1.055 215 DIB 244 0.4 134 0.959 250-285INNROAD ® 188 — 122 1.025 210-260 Protect DIP 216 DIA 272

DESCRIPTION OF THE FIGURES

FIG. 1: mass percentage of loss of volatile compound (Rhodiasolv® RPDE(continuous line), Rhodiasolv® DIB (dotted line), INNROAD® Protect(alternating dots and dashes) and Greenflux® SD (discontinuousline—dashes)) as a function of time at 85° C. in the binder of example 1

FIG. 2: mass percentage of loss of volatile compound (Rhodiasolv® RPDE(continuous line), Rhodiasolv® DIB (dotted line) and Greenflux® SD(discontinuous line—dashes)) as a function of time at 85° C. in thebinder of example 2

FIG. 3: mass percentage of loss of volatile compound (Rhodiasolv® DIB(dotted line) and Rhodiasolv® IRIS (discontinuous line—dashes/points))as a function of time at 85° C. in the binder of example 3

EXAMPLE 1: FLUXED BINDERS FOR SURFACE DRESSINGS

The following binders are prepared:

TABLE 2 T0 C1 C2 L1 L2 L3 L4 bitumen Supplier ESSO Grade 70/100 fluxantName — Petroleum (1) RPDE DIB INNROAD ® DIP DIA Protect Content (% by 06.2 4.5 6.2 5   6   6.5 weight relative to the weight of the binder)Adhesion Name — Impact 9000 (2) dope Content (% by 0 0.3 0.3 0.3 0.3 0.30.3 weight relative to the weight of the binder) (1) Greenflux ® SD soldby TOTAL (2) fatty tallol amides, N-[(dimethylamino)-3propyl] sold byINGEVITY

Binder T0 is a non-fluxed binder, which is used as a control enablingthe properties of the binder according to the invention to be comparedto the binder without addition of compound according to the invention.Binders C1 and C2 are fluxed binders, which are used as comparativeexamples. Binders L1 and L2, L3, and L4 are binders according to theinvention.

The properties of the binders before/after stabilisation and the resultsof the adhesiveness of the binders to the aggregates are given in thefollowing table:

TABLE 3 T0 C1 C2 L1 L2 L3 L4 Before stabilisation STV pseudo-viscosity40° C., 10 mm, s — 440 484 459 468 483 502 Penetrability at 25° C., 1/10mm 78 — — — — — Ball-Ring Temperature, ° C. 46.2 — — — — — Afterstabilisation Mass loss after stabilisation — 3.0% 3.9% 4.9% 4.4% — —Penetrability at 25° C., 1/10 mm — 124 62 92 66 — — Ball-RingTemperature, ° C. — 43.0 51.0 45.4 47.6 — — Adhesiveness to the Vialitplate 5° C. + viadop PX10051 40 g/m² Aggregates 6/10 La Meilleraie -washed and dried Fallen and not marked — 7 8 5 0 — — Fallen and marked —39 90 42 50 — — Bonded to the plate — 54 2 53 50 — —

Stabilisation of the fluxed bitumens is accomplished according to theprotocol described in standard NF EN 13074 1.2 (April 2011). All thetests are conducted according to the protocol described in the standardscited in reference, and explained above.

It is observed that the binders according to the invention enablesatisfactory results to be obtained in terms of adhesiveness and fluxing(observed through the viscosity).

In addition, the binders according to the invention recover theirproperties before fluxing, observed through penetrability and theball-ring temperature.

These results show that the binders according to the invention enablehard surface dressings to be obtained in a short time, allowing fastre-opening to traffic.

As a comparison, it should be noted that Rhodiasolv® RPDE, which doesnot satisfy formula (I), although it is a volatile compound, does notenable satisfactory adhesiveness to be obtained. Indeed, only 2% of theaggregates remain bonded to the plate. Binder C2 does not have aconsistency enabling it to wet the aggregates satisfactorily.

The evaporation curves (mass loss of fluxant as a function of time) forbinders C1, C2, L1 and L2 without stabilisation are reproduced inFIG. 1. It is observed that the evaporation kinetics of binders C1 andL1 are similar, whereas in binder C2 the fluxant has evaporated veryrapidly. Binder L2 has an evaporation profile which is intermediatebetween those of binders C1 and C2.

EXAMPLE 2: FLUXED POLYMER BINDERS FOR SURFACE DRESSINGS

The following binders are prepared:

TABLE 4 C3 C4 L5 Polymer Supplier Eurovia (1) bitumen Grade 50/70bitumen including 3% by weight, relative to the total weight, of linearSBS polymer, cross-linked by sulphur fluxant Name Petroleum RPDE DIB (2)Content (% by weight 15.0 12.0 13.5 relative to the weight of thebinder) Adhesion Name Impact 9000 (3) dope Content (% by weight 0.3 0.30.3 relative to the weight of the binder) (1) this binder has a cohesiongreater than or equal to 1.3 J/cm², as measured according to standard NFEN 13588 of July 2008 after stabilisation according to standards NF EN13074-1 and 13074-2 (2) Greenflux ® SD sold by TOTAL (3) fatty tallolamides, N-[(dimethylamino)-3propyl] sold by INGEVITY

Binders C3 and C4 are fluxed polymer binders, which are used ascomparative examples. Binder L5 is a binder according to the invention.

The properties of the binders before/after stabilisation are given inthe following table:

TABLE 5 Specifications (EN 15332, C3 C4 L6 August 2013) Beforestabilisation STV pseudo-viscosity 83 82 84 50° C., 10 mm, s Afterstabilisation Mass loss after stabilisation 11.0% 11.1% 10.2%Penetrability at 114 46 119 ≤120 25° C., 1/10 mm Ball-Ring Temperature,51.2 60.8 49.5 ≥49 ° C. FRAASS brittle point, ° C. — — −18 ≤−15

Stabilisation of the fluxed bitumens is accomplished according to theprotocol described in standard NF EN 13074 1.2 (April 2011). All thetests are conducted according to the protocol described in the standardscited in reference, and explained above.

It is observed that even for highly modified binders the evaporation ofthe fluxant is suitable, and enables stabilised binders satisfying thespecifications according to standard EN 15322 of August 2013 to beobtained.

The evaporation curves (mass loss of fluxant as a function of time) forbinders C3, C4, and L3 without stabilisation are reproduced in FIG. 2.It is observed that the evaporation kinetics of binders C3 and L3 aresimilar whereas in binder C4 the fluxant has evaporated very rapidly.

EXAMPLE 3: FLUXED POLYMER BINDERS FOR SURFACE DRESSINGS

The following binders are prepared:

TABLE 6 C5 L6 bitumen Supplier Eurovia (1) Grade 70/100 bitumenincluding 3% by weight, relative to the total weight, of linear SBSpolymer, cross-linked by sulphur fluxant Name IRIS DIB Content (% byweight 7.0 8.02 relative to the weight of the binder) Adhesion NameImpact 9000 (1) dope Content (% by weight 0.3 0.3 relative to the weightof the binder) (1) this binder has a cohesion greater than or equal to 1J/cm², as measured according to standard NF EN 13588 of July 2008 afterstabilisation according to standards NF EN 13074-1 and 13074-2 (2) fattytallol amides, N-[(dimethylamino)-3propyl] sold by INGEVITY

Binder C5 is a fluxed polymer binder which is used as a comparativeexample. Binder L6 is a binder according to the invention.

The properties of the binders before/after stabilisations and theresults of the binders' adhesiveness to the aggregates are given in thefollowing tale:

TABLE 7 Specifications EN 15322, C5 L6 August 2013 Before stabilisationSTV pseudo-viscosity 379 367 250-500 40° C., 10 mm, s Afterstabilisation Mass loss after stabilisation 5.8% 5.9% Penetrability at62 84 ≤150 25° C., 1/10 mm Ball-Ring Temperature, 50.4 48.4 ≥43 ° C.FRAASS brittle point, ° C. −13 −15 ≤−14 (specific specifications)Adhesiveness to the Vialit plate 5° C. + viadop PX10051 40 g/m² 6/10ESCHAU aggregates - washed and dried Fallen and not marked 63 11 Fallenand marked 37 20 Bonded to the plate 0 69

Stabilisation of the fluxed bitumens is accomplished according to theprotocol described in standard NF EN 13074 1.2 (April 2011). All thetests are conducted according to the protocol described in the standardscited in reference, and explained above.

It is observed that the binder according to the invention enablessatisfactory results to be obtained in terms of adhesiveness and fluxing(observed through the viscosity). In addition the binder according tothe invention has penetrability, ball-ring temperature and FRAASSbrittle point properties in accordance with the specifications. Theseresults show that the binder modified according to the invention enableshard surface dressings to be obtained in short times, allowing fastre-opening to traffic.

As comparison, it should be noted that Rhodiasolv® IRIS, which does notsatisfy formula (I), although this is a volatile compound, does notenable satisfactory adhesiveness to be obtained. Indeed, no aggregatesremain bonded to the plate and 63% of the aggregates fall without beingmarked. Binder C5 does not have a consistency enabling it to wet theaggregates satisfactorily. However, if the evaporation curves arecompared for C5 and L6, the IRIS and DIB compounds have similarproperties (FIG. 3). These results show that the evaporation curve ofthe compounds in the bitumen is not the only parameter enabling afluxant to be chosen which allows the goals of the invention to beattained.

EXAMPLE 4: EMULSIFIED FLUXED POLYMER BINDERS FOR SURFACE DRESSINGS

The following binders are prepared:

TABLE 8 C6 L7 L8 Polymer Supplier Eurovia (1) bitumen Grade 70/100bitumen including 2.6% by weight, relative to the total weight, oflinear SBS polymer, cross-linked by sulphur fluxant Name Petroleum DIBInnroad ® (2) Protect Content (% by weight 5.4 5.4 5.4 relative to theweight of the binder) (1) this binder has a cohesion greater than orequal to 1.3 J/cm², as measured according to standard NF EN 13588 ofJuly 2008 after stabilisation according to standards NF EN 13074-1 and13074-2 (2) Greenflux ® SD sold by TOTAL

Binder C5 is a fluxed polymer binder which is used as a comparativeexample. Binders L7 and L8 are binders according to the invention.

The properties of the binders before stabilisation are given in thefollowing table:

TABLE 9 C6 L7 L8 dynamic viscosity, mPa · s (NF EN 13302) 100° C. 20231962 1470 120° C. 641 635 500 140° C. 271 219 49.5 160° C. 135 132 117

Binders L7 and L8 have a viscosity comparable to that of the referencebinder, C6.

These binders C6, L7 and L8 were emulsified using the sameemulsification method, with the same surfactant (HCl/amine). Cationicemulsions are manufactured.

The properties of the binder emulsions are given in the following table:

TABLE 10 Emulsion based Emulsion based Emulsion based on C6 on L8 on L9Pseudo-viscosity (NF EN 12846-1) STV 40° C., 13 11 12 4 mm, s STV 40°C., 160 117 134 2 mm, s Homogeneity by sieving (NF EN 1429) Non-passingat 0.04 0.03 0.02 0.500 mm Non-passing at 0.28 0.19 0.18 0.160 mmStorage stability by sieving (NF EN 1429) N (days) 7 7 7 LASERgranulometry (Malvern): MEI Median diameter 2.98 2.86 2.70 (μm) Dynamicviscosity (NF EN 13302) A 40° C. (mPa · s) 2 s⁻¹ 6.0% 2 s⁻¹ 4.4% 2 s⁻¹5.1% 300 mPa · s 220 mPa · s 255 mPa · s 20.4 s⁻¹ 45.4% 20.4 s⁻¹ 34.3%20.4 s⁻¹ 38.9% 226 mPa · s 171 mPa · s 194 mPa · s 34 s⁻¹ 69.7% 34 s⁻¹53.2% 34 s⁻¹ 60.1% 210 mPa · s 160 mPa · s 180 mPa · s Breaking index(NF EN 13075-1) Sikaïsol 47 34 51 Forshammer 66 48 71 Settling (NF EN12847) 7 days, 25° C. 0.4 1.1 0.6

The properties of the emulsions are compliant with the expectedspecifications. The properties of the emulsions with binders L7 and L8are comparable to those observed for the emulsion with binder C6.

For each of these emulsions the adhesiveness was determined by a waterimmersion test according to standard NF EN 13614 (June 2011) with 6/10DUSSAC aggregates (200 g washed and dried). The results are given in thefollowing table:

TABLE 11 Emulsion Emulsion Emulsion based on C6 based on L7 based on L8Aggregate 6/10 DUSSAC washed/dried Mineralogical nature Diorite Residualaggregate/binder 200/10 200/10 200/10 mass ratio Coating Good Good GoodRating (% of covering) 90 90 90

A satisfactory coating (90% of surface covered after immersion in water)was obtained with 10 g of residual binder for each of the emulsions.

The emulsions were stabilised according to the protocol described in theintroduction. The results are given in the following table:

TABLE 12 Emulsion Emulsion Emulsion based based based on C6 on L7 on L8Specifications Penetrability at 58 64 41 <100 25° C. (1/10 mm) Ball-ringtemper- 56.8 55.2 59.8 ≥50 ature (° C.)

The properties of the stabilised emulsions show a slightly lowerevaporation of the DIB compared to the petroleum fluxant and a fasterevaporation of the Innroad® Protect compared to the petroleum fluxant.The presence of residual DIB is observed in binder L7.

EXAMPLE 5: BITUMINOUS CONCRETES WITH EMULSION

Bituminous concretes with emulsion are prepared with the followingformulae:

TABLE 13 BBE I1 BBE I2 BBE I3 BBE C1 BBE C2 BBE C3 Solid 0/4 Uzercheaggregates mineral 4/6.3 Pagnac fraction 6/10 Pagnac pre-lacquered with1.8 pph of emulsion Added 7.1 pph emulsion Fluxant - 0.3 pph 0 contentFluxant - DIB 80/20 Innroad ® Oleoflux ® Greenflux ® — nature blend byProtect SD weight of DIB/RPDE Theoretical 5.0 pph 5.0 pph 5.0 pph 5.3pph 5.0 pph 5.0 pph residual anhydrous binder content

“pph” means “parts per hundred by weight” compared to the weight of thesolid mineral fraction.

The pre-lacquering or contributed emulsion is in both cases a cationicemulsion. In both cases bitumen emulsions are used including a 70/100bitumen as a binder. In both cases bitumen emulsions are used with abinder content of 65% by weight, compared to the total weight of theemulsion.

The fluxant is introduced by spraying at the end of the mixing.

TABLE 14 BBE BBE BBE BBE BBE I4 I5 C4 C5 C6 Solid 0/2 Dussac + 2/6Dussac + mineral 6/10 Dussac fraction Added 7.7 pph emulsion Fluxant -0.3 pph 0 content Fluxant - DIB INNROAD ® Oléoflux ® Greenflux ® —nature Protect SD Theoretical 5.0 5.0 5.3 5.0 5.0 residual pph pph pphpph pph anhydrous binder content

“pph” means “parts per hundred by weight” compared to the weight of thesolid mineral fraction.

The pre-lacquering or contributed emulsion is in both cases a cationicemulsion. In both cases bitumen emulsions are used including a 70/100bitumen as a binder. In both cases bitumen emulsions are used with abinder content of 65% by weight, compared to the total weight of theemulsion.

The fluxant is introduced by spraying at the end of the mixing.

In the case of the Uzerche-Pagnac formulae, the compactability (PCG),the modulus and the workability of these bituminous concretes withemulsion are evaluated. The results for the Uzerche-Pagnac formulae aregiven in the following tables:

TABLE 15 PCG % of voids as a function of a number of gyrations 5 10 1520 25 30 40 50 60 80 100 120 150 200 BBE I1 23.3 20.0 18.2 17.0 16.115.3 14.2 13.4 12.7 11.7 10.9 10.3 9.5 8.6 BBE I2 24.9 21.7 19.9 18.717.8 17 16 15.1 14.4 13.4 12.6 12 11.2 10.3 BBE I3 23.9 20.7 19 17.816.8 16.1 15 14.1 13.4 12.4 11.6 11 10.3 9.4 BBE C1 23.7 20.5 18.6 17.416.5 15.8 14.6 13.7 13.0 12.0 11.2 10.6 9.8 8.8 BBE C2 24.1 21.2 19.117.9 17 16.3 15.2 14.3 13.7 12.6 11.9 11.3 10.6 9.7 BBE C3 27.1 23.821.9 20.7 19.8 19.1 18 17.1 16.5 15.5 14.7 14.1 13.4 12.5

The compactability results demonstrate the ability of compound (I),alone or in combination with compounds (II), to improve the compactingof the bituminous concrete with emulsion, and to reduce the void contentrelative to the same formula without fluxant (BBE C3).

TABLE 16 Changes of the Modulus (MPa) 10° C. 124 ms conservation 35° C.20% RH % of voids 3 days 7 days 14 days 21 days (gamma bench) BBE I11039 1375 1402 1533 15 ± 1 BBE I2 1078 1337 1341 1554 15 ± 1 BBE I3 11851378 2179 15 ± 1 BBE C1 252 455 491 578 15 ± 1 BBE C2 820 1109 1313 146315 ± 1

Compound (I), alone or in combination with compound (II), allows asatisfactory increase of consistency of the bituminous concrete withemulsion compared in particular to reference formula BBE C1. It shouldbe noted in particular that INNROAD® Protect gives the best results.

TABLE 17 Workability (N) after 4 hours BBE I1 332 BBE I2 247 BBE I3 336BBE C1 272 BBE C2 233 BBE C3 187

Compound (I), alone or in combination with compound (II), enables anacceptable workability value to be maintained

In the case of the Dussac formulae, the compactability (PCG) andworkability of these bituminous concretes with emulsion are evaluated.

The results for the Dussac formulae are given in the following tables:

TABLE 18 PCG % of voids as a function of the number of gyrations 5 10 1520 25 30 40 50 60 80 100 120 150 200 BBE I4 27.0 24.0 22.4 21.2 20.419.7 18.7 18.0 17.4 16.6 15.9 15.4 14.8 14.1 BBE I5 26.3 23.2 21.5 20.419.5 18.8 17.8 17.1 16.5 15.6 15.0 14.5 13.9 13.2 BBE C4 25.9 22.8 21.120.0 19.1 18.4 17.5 16.7 16.1 15.3 14.6 14.1 13.6 12.9 BBE C5 26.3 23.521.8 20.8 19.9 19.3 18.4 17.7 17.1 16.3 15.7 15.2 14.6 14.0 BBE C6 27.624.7 23.1 21.9 21.1 20.5 19.4 18.7 18.1 17.3 16.6 16.1 15.5 14.8

The compactability results demonstrate the ability of compound (I) toimprove the compacting of the bituminous concrete with emulsion, and toreduce the void content relative to the same formula without fluxant(BBE C6).

TABLE 19 Workability (N) after 4 hours BBE I4 344 BBE I5 175 BBE C4 241BBE C5 406 BBE C6 641

Compound (I) enables the workability of the bituminous concretes withemulsion to be improved relative to the reference solutions.

EXAMPLE 6: COLD MIX BITUMINOUS MATERIALS (MBCF)

When a 50/70 bitumen grade is used for the formulation of MBCF, thebitumen should be fluxed slightly at the start and late in season, inorder to facilitate the cohesion increase of the MBCF at lowtemperatures. The table below shows the penetrability and ball-ringtemperature variations as a function of the fluxant concentration:

TABLE 20 99.5% 99.2% 99% 98.5% 50/70 + 50/70 + 99% 50/70 + 50/70 +50/70 + 0.5% 0.8% 1% 1% 1.5% 50/70 70/100 INNROAD ® INNROAD ® INNROAD ®Greenflux Greenflux bitumen bitumen protect protect protect SD SDPenetrability 52 80 66 76 83 73 86 at 25° C. in 1/10 mm NF EN 1426Ball-Ring 50.0 45.6 48.4 47.6 46.6 47.6 46.0 temperature, ° C. NF EN1427

The percentages are weight percentages.

Compound (I) enables a change of grade of the bitumen to a lowerconcentration than the reference fluxant to be guaranteed.

1. Method for preparing a bituminous product based on solid mineralparticles in contact with a hydrocarbon binder, comprising a step ofcontacting a composition with solid mineral particles, said compositionincluding a hydrocarbon binder, wherein at least one compound with theformula (I)R¹—X—R—Y—R²  (I) where: R¹ and R², which can be identical or different,are hydrocarbon chains, linear or branched, at C₂-C₁₁; each of —X— and—Y—, which can be identical or different, is an —O—(C═O)— group;—(C═O)—O—; —NR′—(C═O)—, where R′ represents a hydrocarbon atom or analkyl radical at C₁-C₄, or —(C═O)—NR′—, where R′ represents ahydrocarbon atom or an alkyl radical at C₁-C₄, the —R— group is adivalent hydrocarbon chain, at C₁-C₁₀, linear or branched, and possiblyinterrupted by one or more oxygen atom(s) is added as a fluxant agent tosaid composition before, at the same time as or after the step ofcontacting the composition with the solid mineral particles, said stepbeing achieved before complete evaporation of the compound of formula(I) outside the composition.
 2. Method according to claim 1, wherein thecompound of formula (I) is added to the composition including thehydrocarbon binder according to one and/or other of the following 3compatible variants: i. variant 1: the compound of formula (I) is addedat least partly (if variant 2 and/or 3 is also used), or wholly(otherwise), to the composition including the hydrocarbon binder; thecomposition including the compound of formula (I) is then brought intocontact with the solid mineral particles before complete evaporation ofthe compound of formula (I) outside the composition (in other words thesaid compound of formula (I) is still present, at least in part, in thecomposition when it is brought into contact with the solid mineralparticles, preferably in a sufficient quantity in the composition for itto act as a fluxant); and/or ii. variant 2: the compound of formula (I)is added at least in part (if variant 1 and/or 3 is also used), orwholly (otherwise), at the same time as the solid mineral particles, tothe composition including the hydrocarbon binder; and/or iii. variant 3:the compound of formula (I) is added at least in part (if variant 1and/or 2 is also used), or wholly (otherwise), to a pre-blend containingthe solid mineral particles, and the composition including thehydrocarbon binder.
 3. Method according to claim 1, wherein thecomposition also includes a compound satisfying formula (II)R¹—X—R—Y—R²  (II) where: R¹ and R², which can be identical or different,are hydrocarbon chains, linear or branched, at C₁-C₁₁; and where atleast one of R¹, R² is a methyl radical —X— and —Y—, —R— are as definedfor formula (I) in claim
 1. 4. Method according claim 1, wherein thebituminous product is a surface dressing.
 5. Method according to claim4, wherein in formula (I): R¹ and R² are identical, and each is chosenfrom among the ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl,isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl and 2-propylhexylgroups; R is a radical of formula —(CH₂)_(r)—, where r is an averagenumber of between 2 and 4 inclusive.
 6. Method according to claim 1,wherein that the bituminous product is a bituminous concrete withemulsion.
 7. Method according to claim 6, wherein in formula (I): R¹ andR² are identical, and each is chosen from among the ethyl, n-propyl,isopropyl, n-butyl, isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl,isooctyl, 2-ethylhexyl and 2-propylhexyl groups; R is a radical offormula —(CH₂)_(r)—, where r is an average number of between 2 and 4inclusive.
 8. Method according to claim 6, wherein the composition alsoincludes a compound of formula (II).
 9. Method according to claim 7,wherein the composition also includes a compound of formula (II). 10.Method according to claim 6, wherein the hydrocarbon binder includes 1to 25% by weight of the said compound of formula (I), relative to thetotal weight of the hydrocarbon binder and, if applicable, 0.1 to 5% byweight of the said compound of formula (II), relative to the totalweight of the hydrocarbon binder.
 11. Method according to claim 1,wherein the bituminous product is a hot mix or warm mix.
 12. Methodaccording to claim 11, wherein in formula (I) R¹ and R² are identical,and each is chosen from among the ethyl, n-propyl, isopropyl, n-butyl,isobutyl, n-pentyl, isoamyl, hexyl, n-hexyl, isooctyl, 2-ethylhexyl and2-propylhexyl groups; R is a radical of formula —(CH₂)_(r)—, where r isan average number of between 2 and 4 inclusive.
 13. Method according toclaim 11, wherein the hydrocarbon binder includes 1 to 30% by weight ofthe said compound of formula (I), compared to the total weight of thehydrocarbon binder.
 14. Method according to claim 1, wherein thebituminous product is a storable asphalt mix.
 15. Method according toclaim 1, wherein the bituminous product is a cold mix bituminousmaterial.
 16. Method according to claim 5, wherein in formula (I), X andY are esters of diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters ofdiols (—X—=—(C═O)—O— and —Y—=—O—(C═O)—).
 17. Method according to claim7, wherein in formula (I), X and Y are esters of diacids (—X—=—O—(C═O)—;and —Y—=—(C═O)—O—) or esters of diols (—X—=—(C═O)—O— and —Y—=—O—(C═O)—).18. Method according to claim 8, wherein in a compound of formula (II):R¹ and R² are identical and are each methyl; R is a radical of formula—(CH₂)_(r)—, where r is an average number of between 2 and 4 inclusive.19. Method according to claim 18, wherein in formula (II), X and Y areesters of diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols(—X—=—(C═O)—O— and —Y—=—O—(C═O)—).
 20. Method according to claim 9,wherein in a compound of formula (II): R¹ and R² are identical and areeach methyl; group R is chosen from among the following groups: groupR_(MG) of formula —CH(CH₃)—CH₂—CH₂—, group R_(ES) of formula—CH(C₂H₅)—CH₂—, and their blends.
 21. Method according to claim 20,wherein in formula (II), X and Y are esters of diacids (—X—=—O—(C═O)—;and —Y—=—(C═O)—O—) or esters of diols (—X—=—(C═O)—O— and —Y—=—O—(C═O)—).22. Method according to claim 12, wherein in formula (II), X and Y areesters of diacids (—X—=—O—(C═O)—; and —Y—=—(C═O)—O—) or esters of diols(—X—=—(C═O)—O— and —Y—=—O—(C═O)—).